Method for the preparation of bituminous paving compositions and compositions obtained thereby

ABSTRACT

BITUMIOUS PAVING COMPOSITIONS COMPRISING A DRY MINERAL AGGREGATE, A DRY FILLER, A PREHEATED BITUMINOUS BINDER AND HARD ASPHALTS IN THE FORM OF A NON-PREHEATED POWDER ARE PREPARED BY MIXING SAID COMPONENTS IN ANY ORDER AT A TEMPERATURE IN THE RANGE OF ABOUT 140*C. TO ABOUT 210*C., PREFERABLY 180* TO 205*C. THE HARD ASPHALTS PREFERABLY CONTAIN AT LEAST 40% BY WEIGHT OF HARD ASPHALTENES AND NO MORE THAN 30% BY WEIGHT OF CARBOIDS. THE HARD ASPHALTS MAY BE PRECIPATED AROUND PARTICLES OF FILLER BY ADDING NORMAL HEXANE TO A SUSPENSION OF THE FILLER IN A BENZENE SOLUTION OF ASPHALTS.

Aug. 27, 1974 KENNEL ETAL 3332,20)

METHOD FOR THE PREPARATION OF BITUMINOUS PAVING COMPOSITIONS AND COMPOSITIONS OBTAINED THEREBY Filed June 14, 1972 I COMPRESS/VE STRENGTH (BA/PS) s Sheets-Sheet Aug. 27, 1974 KENNEL ETAL 3,832,200

METHOD FOR THE'PREPARATION 0F BITUMINOUS PAVING COMPOSITIONS AND COMPOSITIONS OBTAINED THEREBY Filed June 14, 1972 6 Sheets-Sheet 2 5477605 L/F (/va. 0% 676263) 5 35C I Z7 bars 0 0 Mr I l7bars 3 Ohms 3,510

Aug. 21, 1974 Filed June 14 M. KENNEL A I 3,832,200 METHOD FOR THE PREPARATION OF BITUMINOUS PAVING COMPOSITIONS AND COMPOSITIONS OBTAINED THEREBY 1972 1 6 Sheets-Sheet co/w pess/ 1/5 arms/v6 77/ (54/?5) TEMPQQATK/R' 3,832,200 METHOD FOR THE PREPARATION OF BITUMINOUS PAVING 1 v COMPOSITIONS AND, COMPOSITIONS OBTAI Filed June 14. 1972 Aug. 27, 1974 M, KENNEL ETAL NED THEREBY 6 Sheets-Sheet t ammo mwc Aug. 27, 1974 KENNEL'EI'AL 3,832,200

METHOD FOR THE PREPARATION OF BITUMINOUS PAVING COMPOSITIONS AND COMPOSITIONS OBTAINED THEREBY Filed June 14. 1972 6 Sheets-rSheet COMPRESS/VE STRf/VGTA (BARS) LCPC CRUSH/N6 19o STRENGTH (5/225) 5% 160 150 140 m 120 110 FIG. 6

, t 8.5 as/05,? 6 /1273 5 Y 1405/ 6/! T) Aug. 27, 1974 KENNEL ETAL 3,832,200

METHOD FOR THE PREPARATION OF BITUMINOUS PAVING COMPOSITIONS AND COMPOSITIONS OBTAINED THEREBY Filed June 14. 1972 6 Sheets-Sheet 6 7 III 6 T7 5 T8.

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em/05 6 4273 5r Was/W5) TIRE I Y//// /4 SCALE 10 f3 m [-75.8 SCALE1 United States Patent Oflice Patented Aug. 27, 1974 US. Cl. 106-281 R 5 Claims ABSTRACT OF THE DISCLOSURE Bituminous paving compositions comprising a dry mineral aggregate, a dry filler, a preheated bituminous binder and hard asphalts in the form of a non-preheated powder are prepared by mixing said components in any order at a temperature in the range of about 140 C. to about 210 0, preferably 180 to 205 C. The hard asphalts preferably contain at least 40% by weight of hard asphaltenes and no more than 30% by weight of carboids. The hard asphalts may be precipitated around particles of filler by adding normal hexane to a suspension of the filler in a benzene solution of asphalts.

This application is a continuation-in-part application of US. Ser. No. 98,974 filed Dec. 17, 1970, now abandoned.

This invention relates to a method for the preparation of bituminous paving compositions having improved mechanical properties: It also relates to superior bituminous paving compositions prepared by this method.

Bituminous paving compositions comprise an aggregate, a bituminous binder and a filler. The aggregate is composed of the granular materials which are retained by screens of French Standard AFNOR 20 but are not retained by screens in the range AFNOR 21 through 42. The bituminous binder used for the manufacture of paving compositions comes from coal or petroleum; it is composed of asphaltenes, malthenes and resins which are products of more or less polar intermediate character. The filler is composed of particles whose diameter is less than 80 microns and which consequently pass through the AFNOR 20 mesh screen.

In the description and the claims which follow, the term hard asphalts denotes substances high in hard asphaltenes and refers to products containing at least 40% by weight of hard asphaltenes such as are manufactured on a large-scale from a variety of raw materials including crude oil distillation residues, propane deasphalting tars, and residues enriched with synthetic asphaltenes by oxidation with air or sulfur. By asphaltenes we mean products soluble in carbon disulfide precipitated in the cold or separated with the aid of heat from bituminous materials containing them, by means of saturated low-boiling hydrocarbons, more particularly pentanes, hexanes, heptanes or mixtures thereof. The material which is insoluble in normal heptane as determined in accordance with standard LP. 143/57 is denoted by the term hard asphaltenes. The fractions from the range of products having the lowest molecular weights which can be precipitated or separated by pentanes but not by normal-heptane are referred to as resins. The molecular weight of the hard asphaltenes (Mn) determined by vapor pressure osmometry is higher than 2000. The other asphaltenes have a lower molecular weight (Mn) lying between 700 and approximately 2000; they can be separated by saturated hydrocarbons boiling lower than normal-heptane, but also by polar solvents such as butanol, isopropanol, ethyl ether, etc.

The softening point for hard asphalts thus defined varies within fairly broad limits depending upon the proportion of hard asphaltenes to resins; it can be defined as the temperature at which the particles cling together and can be measured for example on a heated metal block (Maquenne block). The softening point can vary between 120 and 200 C. and even more as the hard asphaltene coritent varies from 40 to The use of very hard binders have been suggested for inproving certain mechanical properties of paving compositions. However the use of very hard binders does not necessarily improve the whole of the mechanical properties 'bf the paving compositions. Moreover the harder the binder, the more heat is required in the preparation of the paving compositions.

Itis also known that molded objects such as bricks, tiles, slabs, sheets and piping can be made by addition of an aggregate with filler to a mixture of oil and asphaltenes. British Pat. 1,127,847 relates to the preparation of such articles. The composition giving the mixture the best crushing strength is one wherein the ratio of oil to asphaltenes by weight is equal to 20/ 80; and wherein the ratio of filler to aggregate is 20 parts by weight of filler to 80 parts by weight of aggregate. Lowering of the filler content has detrimental effects. It must be noted that the oil used in British Pat. 1,127,847 is only a diluent and not a standard bituminous binder, such as is used in the present invention, in that it has an appreciably lower asphaltene content. Moreover the low oil and the high filler contents make the compositions described in the aforesaid patent unsuitable for roadmaking.

Numerous patents are known whose object is the preparation of bituminous paving compositions at ordinary or rather low temperatures. But all of them have many obvious disadvantages in practice, particularly in roadmaking. U.S. Pats. 1,940,645; 2,220,670 and 3,074,807 are three examples thereof. U.S. Pat. 1,940,645 relates to a bituminous paving composition whose binder is prepared by mixing three components: a preferably volatile diluent, a conventional binder and a liquid or powdered asphalt which can be a blown asphalt or a very hard asphalt. such as Gilsonite. This process is not in general use, since it requires evaporation of the diluent at ordinary temperatures and cannot therefore be used to make paving compositions in special demand in modern road building engineering; furthermore, the mixing of the constituents of the paving composition at ordinary temperatures does not lead to a satisfactory dispersion of the asphaltenes in the binder andthe optimization of performance characteristics. US. Pat. 2,220,670 relates to a bituminous paving composition prepared by mixing an aggregate coated with a substantially non-volatile highly aromatic, non-parafiinic oil which is fluid at normal temperature with a powdered bituminous binder which is not a hard asphalt powder; the mixing is done at normal temperature and the oil is a liquid fluxing oil and not a conventional binder. US. Pat. 3,074,807 relates to a two stage process of making a bituminous paving composition consisting of an aggregate coated with a bituminous binder, liquid at ambient temperature, and a powdered natural asphaltite. In a first stage these components are mixed at a temperature lower than the critical amalgamation temperature of the natural asphaltite to the binder, i.e. less than about F., whilst the bituminous binder used has a relatively high portion of volatile components; in the second stage the composition is amalgamated either by the application of pressure or by subjecting it to high temperatures for prolonged periods.

U.S. Pat. 2,349,446 relates to a process of making bituminous paving compositions which consists in preparing a first batch portion by mixing coarse aggregate particles with bituminous cement in liquid form, and a second batch portion by mixing fine aggregate particles with fluxing oil and with powdered hard bitumen and thereafter bringing the two batches together and mixing them; this process requires two different binders:' one in each batch; the binder used in the second batch is a diluent rather than a conventional binder, and the temperature of mixing the two batches together is too low to assure a sufficient degree of amalgamation of the composition.

The use of a diluent is not without drawbacks. It demands very high proportions of asphaltenes which are generally expensive. As it will be seen hereinafter, the bituminous paving compositions prepared according to the process of the invention have improved mechanical properties and a better stability without overdosing them with asphaltenes.

The mechanical properties of the paving composition can very between relatively wide limits depending on the nature of the binder (viscosity, modulus of rigidity, chemical stability at the paving temperature): for instance the resistance measured at 18 C. by the LCPC method for bitumens having the same penetration of 80/ 100 can vary between 40 and 80 bars. Depending on the temperature susceptibility of the binders used, the relative differences in properties of the paving compositions may vary or even become reversed, if the comparisons are made at temperatures higher or lower than 18 C.

The properties of the binder as a function of temperature are not however the only factors which determine the resistance of a paving composition. The quantity of the filler is also important. A number of materials can serve as filler: sand, limestone, slags, lime, vulcanized rubber, ground and screened coke obtained by any known method from coal or oil; a mixture of fillers can also be used.

As Tunniclitf teaches (Proceedings Association of Asphalt Paving Technologists, vol. 36, pages 114-156) the resistance of bituminous paving compositions is essentially determined by:

(a) modulus of rigidity of the mastic (binder-i-filler) which is a function of the modulus of rigidity of the binder itself and its fillerization value (ratio of filler/ binder);

(b) relative volume of the remaining voids in the paving composition expressed by the void coefficient as Percent volume of binder+percent volume of filler Percent volume of voids in the aggregate without filler.

As will 'be evident later from the description of our invention, however, we have found that it is possible to produce paving compositions having the same void coefficient but with widely different and superior resistance properties.

An object of the present invention is to provide superior bituminous paving compositions and a method whereby they can be prepared.

According to the invention superior bituminous paving compositions comprising a mineral aggregate, a bituminous binder and a filler, are prepared by the addition of hard asphalts during the preparation of the composition, the mixing temperature being equal to at least 140 C. and the components being mixed in any order.

The present invention furthermore provides a method for preparing superior bituminous paving compositions comprising an aggregate, a bituminous binder and a filler, by precipitating the hard asphalts around the filler before the latter is blended with the aggregate and the preheated binder.

It has now been ascertained that certain tests are good indicators of the subsequent behavior of the paving compositions under working conditions. Specifically the tests comprise fatigue strength, compressive or tensile strength and resistance to rutting.

These tests, hereinafter to be described in detail within the scope of working examples of the invention, consist in the case of the first test: applying a constant force of rotary flexion to a test piece at a constant frequency; in the case of the second test: imposing an axial stress of compression or elongation on a test piece to produce a linear distortion; and in the case of the third test: subjecting a slab of the paving composition to the periodic passage of an inflated pneumatic tire under constant load and frequency.

We have found that superior paving compositions can be prepared by regulating the ratio between the volume of the hard asphalts and that of filler in such a manner as to optimize the desired properties of the composition for the specific purpose for which it is intended. It has been found in this connection that the ratio volume hard asphalts-l-filler volume hard asphalts has an optimum value for each temperature range for a given binder and aggregate which provides maximum life in the rotative fiexion test under steady load and frequency.

The hard asphalts usable within the scope of this invention must be in a sufficiently divided form so that their introduction into the paving composition will not involve any heterogeneity of composition in the binder. A hard asphalt particle size of the same order of magnitude as that of the filler has been found to be particularly advantageous for the method of this invention. However, such size is not a critical one and it will be sufiicient if the hard asphalts used come in the form of particles whose size does not exceed that of the finest portion of the aggregate. The finer the hard asphalts, the more quickly their homogeneous dispersion in the binder upon mixing.

Certain raw materials such as those obtained from cracking, visbreaking, hydrocracking residues and pyrolysis of oxidized or polymerized residues can contain carboids. Because of their low hydrogen content, carboids are insoluble in carbon disulfide; they are also precipitated by low boiling saturated hydrocarbons. Carboids have a softening temperature higher than the hard asphaltenes and can even be practically infusible. The term hard asphalts also covers products containing carboids but it has been found that in the manufacture of superior paving compositions of this invention, the action of the carboids is less effective than that of the hard asphaltenes. The amount of carboids in the hard asphalts should preferably be less than 30% by weight.

Natural asphalts can also be used as hard asphalts after they have been ground to a powder.

The bituminous binder used comes from coal or oil; it is obtained by generally known processes.

The invention makes it possible to prepare superior bituminous paving compositions from relatively soft binders (with a penetration of /1100 for example); the mechanical properties of such compositions are superior to those obtained for paving compositions prepared, by conventional methods, from harder binders (of 20/30 penetration, for example).

The possibility to use soft rather than hard binders has many obvious advantages. For instance, soft binders are more readily stored, handled and transported than the more viscous hard binders. They are also easier to apply. Further, they make possible savings in the heat required in preparing the paving compositions, since soft binders are workable at lower temperatures than hard binders.

One unexpected finding is that despite their diiferent natures, to a very large extent, the filler can advantageously be replaced by hard asphalt; this substitution yields bituminous paving compositions of far superior performance characteristics.

It has also been found that in order to obtain optimum fatigue properties, the filler and hard asphalt proportions to be added when preparing composition must not be taken at random; the optimum proportion depends on the mean service temperature for the pavement. Thus, for example, if two compositions are considered, one of which for a mean service temperature of 20 C. and the other for 5 C., the ratios between the quantity in terms of volume of hard asphalts introduced into the coating and the sum of the volumes of hard asphalts plus fillers, which correspond to the optimal fatigue properties are 0.5 and 0.25 respectively. The present invention allows determination of the optimum proportions mentioned above by carrying out rotative flexion tests at steady load and frequency on test pieces of bituminous paving compositions of various formulations. The invention lends itself, consequently, to the manufacture from a binder of given hardness, of paving compositions with better mechanical properties for the range of temperatures for which the composition is intended.

The mixing temperature of the ingredients assumes considerable importance and produces an unexpected effect: in fact, while the mixing temperature has in practice only a slight influence on the mechanical properties of paving compositions made by conventional methods, it has, on the contrary, a great effect on the quality of the paving compositions made according to the present invention (this result will be illustrated by Example V). In practice, it is found advantageous to carry out the mixing step at temperatures higher than those used with conventional formulations in order to assure a good dispersion of hard asphalts in the hydrocarbon binder. The mixing temperature must be at least 140 C.; nevertheless, it is not worth while proceeding to mix at temperatures higher than 210 C., since in the first place, the gain in mechanical strength is low, and secondly, the hard asphalts as well as the binder are liable to become deteriorated at such high temperatures. We have found that for most parafiinicasphaltic crudes, such as those of the Middle East, the preferred range is between 180 and 205 C. It has also been found that the mixing temperature must increase when the softening point of the hard asphalts rises and that, for a given softening point, finer particles allow a relative lowering of such temperature.

The hard asphalts can be introduced into the mixture of binder, aggregate and filler at the end of the mixing operation; in this way the advantage of working with a soft binder as long as possible is maintained. Nevertheless, the addition of the hard asphalts only at the end of the mixing operation is not imperative; they can be added at any stage during the production of the paving composition: thus hard asphalts can be introduced into the binder before its conveyance to the paving sites.

One method of introducing hard asphalts is to precipitate the hard asphalts around the filler by addition, for example, of normal hexane to a suspension of filler in a solution of asphalts in benzene, then adding the filler and hard asphalts to the mixture of aggregate and binder.

Eight figures are attached to the specification.

FIGS. 1, 2 and 3 are graphic representations of the results obtained in Example 111; they relate respectively to the compressive strength and fatigue life measured as a function of R (whereof the definition is given in Table III) and the compressive strength measured as a function of temperature.

FIG. 4 is a graphic representation of the results of Example IV. It relates to LCPC (French Central Highways and Bridges Laboratory) crushing strength at 18 C. as a function of R.

FIG. 5 is a graphic representation of the results of Example VI; it relates to the compressive strength measured as a function of temperature.

FIGS. 6 and 7 are graphic representations of the results obtained in Example V11; they relate respectively to the LCPC crushing strength and the volume of voids both measured as a function of the binder content of the paving composition.

FIG. 8 is a graphic representation of rut profiles obtained in Example VIII,

The invention is further illustrated by the following examples which are mentioned nonlimitatively.

EXAMPLE I The binder used in all of the following tests had a penetration of expressed in tenths of a millimeter (test effected at 25 C., with a 100 gram load applied for 5 seconds, the needle conforming to French Technical Standard N.F.T. 6004). The binder used in Examples I, II and III, is obtained by direct distillation of a Boscan type crude oil of Venezuelan origin.

The hard asphalts result from normal-heptane precipitation of a deasphalting pitch; they are wholly soluble in benzene and in carbon disulfide. They are used in the form of a powder having a particle size less than approximately microns.

The filler is a sand filler obtained by screening sand, or a limestone filler, or an oil coke filler obtained by the fluid coking process, whose properties are as follows: Infusible Wholly insoluble in carbon disulfide Carbon in gram-atoms A bituminous paving composition was produced by the following method: sand 0/3 previously screened, (screening is effected if it is not wished to introduce sand filler or if it is to be introduced in proportions differing from the natural proportions), was oven dried at 150 C. The 9 penetration binder was preheated to the same temperature over a period of 2 hours. The sand was introduced into a temperature-controlled mixer. The cold filler was then dispersed into the sand for 5 minutes as necessary. Then the cold, hard asphalts were introduced. The binder was then added; mixing in the presence of the binder proceeded for 5 minutes, at the end of which time the test pieces were prepared.

For the fatigue strength tests, toroidal test pieces were made having a middle diameter of 30 mm. and end diameters of 45 mm. These toroidal test pieces are made as follows: a volume of 200 cc. of paving composition is introduced into a cold mold and immediately compressed under 15 metric tons pressure by means of two pistons for 30 seconds. After cooling, the test pieces are taken out of the mold and then remain for a sufficient period to allow them to reach thermal equilibrium at the fatigue test temperature.

Cylindrical test pieces, having a diameter of 45 mm. and weight of 300 grams, are made for the compression strength tests; they are compacted under 6 metric tons for 1 minute. The same precautions are observed for stripping from molds and storage as those already stated above.

The fatigue strength tests consist in imposing on the toroidal test piece, under steady load and temperature, torsion at a frequency of 25 cycles per second. The toroidal test piece is placed in such a way that its axis will be vertical when no load is exerted thereon; the bottom of the test piece is engaged in a mandrel which, at the time of the test, is driven in rotary motion around its vertical axis; the speed of rotation is adjustable. Around the top of the test piece, a metal rim is placed, around which a ball bearing is engaged. This device allows a steady transverse tensile stress to be applied to the test piece. The number of cycles made by the test piece at the instant when breakage Melting point n C. 280 takes place is noted, which hereinafter will be called the Insolubles in carbon disulfide, percent (by fatigu lif h b weight) 25 The compression strengt tests consist in su mitting the cylindrical test piece to a crushing force at the steady comgosltlon' Percent (by welght) speed of 50 mm. per minute. The force exerted at the arbon 8289 moment when the test piece breaks is noted. Hydrogen Table I below shows the composition of the various test Oxygen u pieces, together with fatigue life and compressive strength Ash corresponding to each of these compositions; determina- Sulfur tion of these properties was effected at C. Composi- Carbon y Weight) tions in aggregate, filler and hard asphalts are given in R3 0 Hydrogen (by weight) percentage per 100 parts by volume of aggregate, filler Hydmgenfin grammoms) and hard asphalts; the proportion of binder is given for Ratio 0.94 100 parts by weight of aggregate, filler and hard asphalts. Carbon gram'awms) TABLE I Test number 1 2 3 4 5 Com osition (volume) percent:

0 3 sand freed of filler 84 84 84 84 84 Sand filler Limestone tiller.-. Oil coke filler The mechanical properties of compositions 1, 2 and 3 were essentially the same. Fillers of different character, when present in the paving compositions in identical volumes therefore furnish the latter with closely related mechanical properties.

Tests 4 and 5 illustrate the properties of the paving compositions obtained by using the method of the invention. A comparison between the various mechanical properties of these paving compositions and No. 3 shows the considerable increase in fatigue life and compressive strength furnished by application of the invention method. These advantageous results are also found to be obtained by lowering the filler proportion in the paving composition.

EXAMPLE II This example relates to the application of the invention method in the case Where the hard asphalts introduced into the paving composition are not entirely soluble in carbon disulfide.

Bituminous paving compositions were prepared according to the method described in Example I, except that the hard asphalts used were obtained by precipitation from a visbreaking fuel with a straight-run gasoline between 60 C. and 100 C. Visbreaking was eifccted on a vacuum distillation residue of an Iraki crude oil. This produced a fuel having a viscosity of 280 cs. at 50 C. and a xylene equivalent equal to 95.

The precipitate of hard asphalts had the following characteristics:

The hard asphalts were obtained directly in a sufficiently finely divided form for introducing into the paving composition without grinding or screening.

Table II below presents the formulation as well as the mechanical properties of the paving compositions, measured at 20 C. under conditions identical to those described in Example I.

TABLE II Test number 1 7 Composition (volume) percent:

0/3 sand freed of filler 84 84 Sand filler 16 8 Hard asphalts 8 Binder (parts by weight) 8 8 Void coefficient 0. 88 0. 88 Mechanical properties at 20 (3.:

Fatigue life:

Under 7.7 bars (No. of cyeles) 5. 5x10 1X10 7 Under 17 bars (No. oicycles) 6. 0X10 1. 5X10 5 Compressive strength (bars) 110 275 It is established that the introduction of hard asphalts and the concomitant decrease of the proportion of filler in the bituminous paving composition considerably improve the latters mechanical properties.

EXAMPLE III This example relates to the effect of tempearture on the mechanical properties of the paving compositions and the determination of the optimal proportion of hard is made of the curves giving the variation of the fatigue life as a function of the ratio R, together with curves giving the compressive strength.

Values of the ratio R will preferably be selected which lead to a maximum of the fatigue life in the case where the paving composition is intended for the making of road pavements. On the other hand, values of this ratio affording high compressive strength will be selected in the case where the composition is used in the making of molded blocks for the construction of buildings, for example. Values of the ratio R slightly higher than the TABLE III Test number 8 9 10 11 12 13 14 15 16 17 18 19 Com osition (volume) percent:

0 3 Sand freed 0i fill 84 84 84 84 84 84 84 84 84 84 84 84 12 8 4 2 16 12 8 4 16 12 8 4 8 12 14 4 8 12 4 8 8 8 8 8 8 8 8 8 8 8 8 Hard asphalts vol. Hard asphalts VOL 0 0. 0. 50 0. 75 0. 87 0 0. 25 0. 50 0. 75 0 0. 25 0. 50

Plus filler volume Void coefficient 0.88 0. 88 0. 88 0. 88 0.88 0. 88 0. 88 0. 88 O. 88 0. 88 0.88 0. 88

Me h l o erties at; the tem eratfn:% f u 0. 35 0. 35 0. 35 0. as" 0. 20 0. 20 0. 20 0. 20 0. 5 0 5 o, 5 c,

Compressive strength (bars) 45 105 150 5 180 100 190 240 260 240 350 400 Fatigue life (no. of 03 0165)"..- 3.5)(10 3 1. 6X10 5 8X10 5 1. 1X10 5 7X10 5 3. 5X10 3 3X10 4 7. 5X10 4 3X10 4 3. 5X10 3 9X10 5 3. 5X10 3 Under load (bars) 7. 7 7- 7 7- 7 7. 7 7. 7 17 17 17 17 42 42 42 FIGS. 1, 2 and 3 are graphic representations of the results obtained.

FIG. 1 is a diagram of the representative curves of the variation of compressive strength (expressed in bars) as a function of the value R of the ratio of the volume of hard asphalts introduced, divided by the sum of the volumes of hard asphalts and filler introduced. It will be noticed that this sum is constant, since the addition of hard asphalts is made at the expense of the amount of filler.

FIG. 2 is a diagram of the representative curves of the variation of fatigue life as a function of the value R of the ratio defined in connection with FIG. 1. The fatigue life of the test pieces is expressed by the number of cycles effected before breakage, at constant frequency and under a constant load for each test temperature.

FIG. 3 represents a set of curves illustrating the variation of the compressive strength (expressed in bars) in terms of the service temperature of the paving composition.

It can be noted that the compressive strength is an increasing function of the hard asphalt proportions introduced at the expense of the filler in the paving composition, except at the temperature of 5 C. for which there is a maximum breaking load. On the other hand, the fatigue life passes through a maximum when the proportion of hard asphalts increases in the paving composition. The position of this maximum varies with temperature. Thus, paving compositions used at mean temperatures of 5 C., 20 C. and 35 C. have a fatigue life for the value R of the ratio of the volume of hard asphalts to the sum of the volumes of hard asphalts and filler of approximately 0.25, 0.50, 0.75, respectively.

It is therefore possible, knowing the range of tempera tures to which the bituminous paving composition will be subjected during its service, to determine the value of the ratio R which will give the paving composition the highest mechanical properties and to deduce therefrom the amount of filler and hard asphalts suitable to introduce into the paving composition. In order to do this, use

values corresponding to the maxima of the fatigue life at a given temperature, constitute a satisfactory compromise between the requirements of fatigue life and resistance to compression and to creep.

EXAMPLE IV This example relates to formulations for bituminous paving compositions for use in the making of road pavements. These compositions were subjected to the crushing strength test by the test method recommended by the French Highways and Bridges Central Laboratory (LCPC Strength, or Duriez Test). Tests were effected for two different binders: the first was a binder of /100 penetration arising from the dilution of a blown vacuum distillation residue from crude Iraki petroleum with the nonblown residue; the second, much more fluid, was a vacuum distillation residue of Iraki crude oil whose viscosity amounted to 900 cs. at 210 F. or 99 C.

The method of test piece preparation was as follows: the binder brought either to a temperature of 150 C. when dealing with a penetration binder or of C. when handling the vacuum distillation residue was added to the aggregate previously dried at C. After about 15 seconds of mixing, the coke filler, preheated in advance to 140 C. was added; then after approximately 15 seconds, the unpreheated hard asphalts, identical with those described in Example I, were added. After a total mixing time of about 2 minutes, a test piece complying with the standards set by the French Highways and Bridges Central (LCPC) Testhouse was prepared and subjected to the crushing strength test at 18 C.(LCPC crushing strength).

Table IV sets out the formulation of the bituminous paving compositions and their crushing strength at 18 C. The amounts of aggregate, filler and hard asphalts are given as percentages per 100 parts by volume of these three constituents; the proportion of binder is given per 100 parts by weight of these three constituents. The sizes of the constituents of the aggregate are given in millimeters.

TABLE IV Test number 20 21 22 23 24 25 26 27 2s 29 Composition (volume) percent:

/3 sand freed of 611m- 37. 1 37.1 27.1 37 1. 37.1 37.1 37.1 37.1 27.1 57.1 Gravel 3/5. 18.5 18.5 18. 1s. 5 1s. 5 18.5 18. 5 18.5 18.5 18. 5 Gravel 5/8. 18.5 18.5 18. 5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 Gravel 8/12 18. 5 18.5 18. 5 18.5 18.5 18. 5 18.5 18.5 18.5 18.5 6.4 5.6 3.7 1.8 7.4 5.6 3.7 1.8 Hard asphalts 1. 8 3.7 5. 6 7. 4 1. s 3. 7 5. 6 7. 4 Binder:

Bitumen 80/100 (parts by weight).; 6. 2 6.2 6. 2 6. 2 6. 2 Residue under vacuum (parts by welght) 6. 2 6. 2 6. 2 6. 2 6. 2 LQPC crushing strength at 18 C. (kg/cm 3) 41 58 75 95 95 22 27 35 47 58 Void coefiicient 0. 64 0.64 0.64 0. 64 0. 64 0. 64 0. 64 0.64 0. 64 0. 64

FIG. 4 is a set of representative curves of the variation TABLE V of the LCPC crushing strength as a function of the value Aggregate R of the ratio defined in connection with FIG. 1. Pam P1115 Binder e Hard The conclusions to be drawn are analogous to those gcomposl 1on5 finer mum) asphalts expounded in Example III. The curve relative to the In 1 T1, T2, T3 100 6. 5(90) 0 binder is to be compared with the cure relative to the temperature of C. on FIG. 1, although this latter does not shown any maximum. It appears that in the conditions defined above, a coating whose value R of the ratio of the volume of hard asphalts to the sum of volumes of the filler and hard asphalts is in the vicinity of 0.75 and preferably higher, constitutes an excellent road pavement. Doubling of the strength is obtained with the binder for a ratio R of the order of 0.57. On the contrary, the curve relative to the binder constituted by a vacuum distillation residue shows that to attain that same level of mechanical performances, a prohibitive consumption of hard asphalts must be allowed. The curve relative to the binder constituted by a vacuum distillation residue is to be compared with the curve relative to the temperature of 35 C. on FIG. 1, the binder being in this case harder: the larger R values are the most favorable.

EXAMPLE V This example relates to the effect of the mixing temperature of the constituents of bituminous paving compositions.

The binder used in this example, as well as in Examples VI, VII and VIII had a penetration of it was the product from the dilution of a blown vacuum distillation residue from Kuwait crude petroleum with the same nonblown residue.

Three control paving compositions T T T of the same composition (without hard asphalts) were made; the mixing temperatures were t t t respectively. Three paving compositions I, II, III of like composition with hard asphalts were also made; the mixing temperatures were respectively t t t;;.

The method used was as follows: to 6.5 parts by Weight of 90 penetration binder kept at the temperature I or t or i 100 parts by weight of the aggregate and filler mixture (previously dried at temperature t t or were added, being distributed in the following manner: 0/3 sand (33.6% by volume), gravel (30% by volume), 45 gravel (20% by volume), 8A2 gravel (20% by volume) and sand filler (6.4% by volume) in due course. The hard asphalts were then added in the form of a carefully ground, unpreheated powder. Mixing proceeded for 1 minute at temperature t or t or t The hard asphalts were obtained by treatment at 20 C. of a vacuum distillation residue of a crude Iraki oil with a low-boiling gasoline. After washing to remove oil, the solvent was evaporated from the hard asphalts. A product resulted whose solubility in heptane was less than 25%, whose solubility in benzene was higher than 90%, whose true density was around 1.15 and whose melting point was higher than 145 C. After grinding, microscopic observation disclosed that the major portion of the particles had a diameter less than 20%.

The composition of the paving compositions expressed in parts by weight is shown in Table V. In all of these tests, the void coefficient is about 0.64.

TABLE VI Paving compositions Tl T2 T3 I II III Mixing temperature (in C.) 150 180 210 150 180 210 Compressive strength (in bars)- 50 52 56 87 111 122 This table shows the increase in compressive strength furnished by the addition of hard asphalts in the coatings. The gain is maximum if mixing is permitted at a higher temperature than for the conventional paving compositions; this increase in temperature gives the conventional compositions only a low, even negligible gain.

EXAMPLE VI This example relates to the eifect of the introduction of hard asphalt powder on the compressive strength of composition test pieces, as a function of the test temperature.

Sample compositions Without hard asphalts T T T T and T were prepared; and compositions IV and V complying with the invention.

Such compositions were prepared as follows: a previously dried aggregate and previously dried filler were added to some binder, all these constituents being identical with what is described in Example V; hard asphalts or Orgon filler consisting of calcium carbonate are then added as the case may be. Mixing lasts for two minutes, the hard asphalts or Orgon filler are introduced after 1 minute of mixing for compositions IV, V T T and T Table VII shows the mixing temperatures and the formulation of the paving compositions in parts by weight.

TABLE VII Mixing Aggregate Binder Void temp. plus sand (pene- Hard Orgon coefii- C.) filler tration) asphalts filler cient Slabs of the compositions were made measuring 50 x 18 x 8 cm. by compacting for 10 minutes with a Proctor rammer, having a stroke of 45 cm., in suitable molds.

Test pieces measuring 4 x 4 x 8 cm. were obtained by cutting the slab to size. After establishing thermal equilibrium at 18 C. these were compressed along their length 13 by means of an Instron press at the speed of cm. per minute; the force at the instant of rupture was noted.

The test results on compositions IV, V, T T T T and T are shown in FIG. 5.

These tests show that at any temperature, coatings IV the optimum quantity of the binder is displaced by the addition of hard asphalts. This phenomenon is most pronounced for series VI.

FIG. 7 assembles the curves representative of the voids in the six series of compositions. They bring out the fact and V according to the invention have a higher crush- 5 that composition series VI is particularly close or coming strength than that of the control compositions. This is pact and therefore has a higher resistance to atmospheric a surprising result: indeed, considering the hardness of agents than the other series. The voids of a composithe binder of composition T and the hardness of the tion are expressed in parts by volume for 100 parts of binder and hard asphalt mixtures of compositions IV 10 volume of the compositionasthe ratio: and V, they are found to be closely related (in the case of T and V) or even practically equal (in the case of T and IV), as Table VIII shows. The comparison of composition IV, V and T shows that the improvement theoretlcal derllsty zfi i is not due to abetter filling of the voids. voids= 100 X rea i y 0 e cPinposltlon real density of composition TABLE VIII Hardness (penetration in tenths ofmm) The theoretical density is calculated from the density Binder plus of each specie appearing in the composition. The real Compositions Binder hard iii i tiiiz density is measured The knowledge of the voids of the compositions permits 3% comparison of the efficiency of the mastics in the tightness (sealing) of the paving compositions.

Table X presents the results for compositions compris- The invention consequently, by using a first binder and 25 ing 6.5 parts by weight (percent wt.) of binder per 100 hard asphalts, allows for the preparation of bituminous parts by weight of mixture of aggregate and sand filler. paving compositions showing better mechanical properties than those of compositions prepared from a second binder of hardness equal to that of the mixture of the TABLE x first binder and hard asphalts, all things otherwise being Parts by volume per equal. Examples V and VI especially illustrate the prog- 3g zg ggf g ress achieved by optimization study of the various factors and particularly of the mixing temperature. C it 22%: Tom EXAMPLE VII Tompos ion 0 inder mastic This example relates to the influence of the introduc- ViITIIII: 33$ tion of powdered hard asphalts on the LCPC crushing gg-g strength of composition test pieces and on the voids in the 7 compositions as a function of the amount of binder.

Six series of bituminous paving compositions were pro- 40 duced, f which fo were contro15( T7, T d T Table X brings out firstly that composition VI has the and two were in accordance with the invention (VI and lowest voids and secondly that equal voids (compositions 11 VII and T7) are obtained by using a lower volume (ap- The method and order of introduction of the compoproximately of total in composition nents were identical with those described in Example These differences would be $1111 greater if the added V; however, the quantity and the penetration of the binder amount of hard asphalts were were variables. The aggregate and sand filler were identical with those used in Example V. Some Orgon filler EXAMPLE VH1 can be added as a supplement. This example relates to the resistance to rutting of the The amount of binder, hard asphalts and Orgon filler compositions according to the invention. were respectively x, y and 2 parts by weight per 100 parts Asphalts paving compositions were produced according by weight of the aggregate and sand filler mixture. The to the method described in Example VI: control compovalue x varies from 5.5 to 8.5 in each series; the ratios sitions T and T and compositions complying with the x/y and x/z are constant in each series. invention, denoted by VIII and DC. Mixing was efiected Table IX shows the mixing temperature and the formuat a temperature of 190 C. lations of these six series of paving compositions, as well Table XI shows the formulations of the compositions as the void coeificients for 6.5 parts by weight of binder. expressed inparts by weight.

TABLE IX Mixing Binder Hard Orgon Void temp. (z) peneasphalts filler coetfi- Composition 0.) tration (y) 1]: eient 190 Yes 3.25 0.76 190 90 Yes No-.- 6.5 0.70 90 No Y 1.625 0.75 25 No Yes 1.625 0.75 160 90 No 0.64 190 25 N 0.64

Test pieces were prepared from the six series of compositions for the purpose of measuring crushing strength TABLE XI at a temperature of 18 C. in air, according to the LCPC 70 Binder Agg strength determination method. plus 2%: 33,;

FIG. 6 is made up of the curves representing these tests. These curves bring out the superiority of the pav- :33 ing compositions according to this invention as against igg g the conventional compositions; they also emphasize that 75 Slabs'of the compositions measuring 50 x 18 x cm. were made by compacting for minutes with a Proctor rammer having a stroke equal to 45 cm.

The test pieces obtained were subjected at room temperature of 50 C. (after establishing thermal equilibrium) to a cyclic passage over their larger surface by an inflated pneumatic tire at a pressure of 5 bars and under a load of 500 decanewtons. After 300,000 cycles, a profile of the rut thus formed is taken up.

FIG. 8 is a representation of these profiles. In this figure, the ordinate scale is 10 and the abscissa scale 1; a pneumatic tire is also shown transversely to give a scale of magnitude of the rut width. This figure confirms the superiority of compositions according to the invention, these being the ones whose final profile differs least from the original profile.

We claim:

1. A method for the preparation of a bituminous paving composition, whose components consist essentially of:

(1) a dry mineral aggregate having a particle size of at least 80 microns,

(2) a dry filler having a particle size of less than 80 microns,

(3) a preheated solid bituminous binder separated from coal or petroleum and consisting essentially of asphaltenes, malthens and resins and (4) hard asphalts in the form of a non-preheated powder and containing at least 40% by weight of hard asphaltenes, the balance being composed of resins and no more than 30% by weight of carboids, the size of the hard asphalt particles not exceeding that of the finest portion of the aggregate, said method comprising mixing said components in any order at a temperature in the range of about 180 C. to 205 C.

2. A method according to claim 1, wherein the hard asphalts have a particle size approximating that of the filler.

3. A method according to claim 1, wherein the volume of non-preheated hard asphalt powder and the volume of filler are such that the value of the ratio of the volume of hard asphalts to the sum of the volumes of hard asphalts and filler approaches, and is preferably higher, than the value of that ratio which, within a specified temperature range for the specific binder and aggregate used, gives the bituminous paving composition maximum life in the rotative flexion test at steady load and frequency.

. 4. A bituminous paving composition prepared by mixing in any order at a temperature in the range of about 180 C. to 205 C. the following components:

(1) a dry mineral aggregate having a particle size of at least microns,

(2) a dry filler having a particle size of less than 80 microns,

(3) a preheated solid bituminous binder separated from coal or petroleum and consisting essentially of asphaltenes, malthenes and resins and (4) hard asphalts in the form of a non-preheated powder and containing at least 40% by weight of hard asphaltenes, the balance being composed of resins and no more than 30% by Weight of carboids, the size of the hard asphalt particles not exceeding that of the finest portion of the aggregate.

5. A bituminous paving composition according to Claim 4 wherein the volume of non-preheated hard asphalt powder and the volume of filler are such that the value of the ratio of the volume of hard asphalts to the sum of the volumes of hard asphalts and filler approaches, and is preferably higher, than the value of that ratio which, within a specified temperature range for the specific binder and aggregate used, gives the bituminous paving composition maximum life in the rotative flexion test at steady load and frequency.

References Cited UNITED STATES PATENTS 1,940,645 12/1933 Fletcher 9423 2,220,670 11/1940 Beckwith et al. 94-23 2,349,445 5/1944 McGrane 106--280 2,349,446 5/1944 McGrane 106-280 2,686,166 8/1954 Taylor 260--28.5 2,921,919 1/1960 Endres et al. 26028.5 3,074,807 1/1963 Dorius et al. l06273 3,253,521 5/1966 Endrcs 9420 JOSEPH L. SCHOFER, Primary Examiner H. J. LILLING, Assistant Examiner U.S. Cl. X.R. 106-284 

